Sulfurized compositions and lubricants containing them

ABSTRACT

A sulfurized composition prepared by sulfurizing a mixture of at least one terpene and at least one other olefinic compound is described. More particularly, sulfurized compositions prepared by sulfurizing a mixture of pine oil and at least one other olefinic compound are described. Such sulfurized compositions are useful as lubricant additive compositions, and more particularly, as additive compositions in industrial and gear lubricants. The compositions when added to lubricants provide lubricants which exhibit improved antioxidant characteristics, nitrile seal compatibility and acceptable color characteristics.

BACKGROUND OF THE INVENTION

This invention relates to new sulfurized compositions of matter whichare suitable particularly for use as lubricant additives, and to methodsfor their preparation. More particularly, the sulfurized compositions ofthe invention are derived from a mixture of at least one terpenecompound and at least one other olefinic compound.

Compositions prepared by the sulfurization of various materialsincluding olefins are known in the art, and lubricants containing thesecompositions also are known. Typical sulfurized compositions prepared byreacting olefins such as isobutene, diisobutene and triisobutene withsulfur under various conditions are described in Chemical Reviews, 65,237 (1965), and in The Chemistry of Organic Sulfur Compounds, Vol. II,Chapter 10, (1966). These products generally are characterized by thepresence of a trithione grouping. A by-product is hydrogen sulfide, andit is frequently taught that it is desirable to remove the hydrogensulfide which is formed. Other publications describe the reaction ofsuch olefins as isobutene, diisobutene and triisobutene with hydrogensulfide to form predominantly mercaptans, and by-products such assulfides, disulfides and higher polysulfides. See, J. Am. Chem. Soc.,60, 2452 (1938); J. Chem. Soc., 1947, 1532; and U.S. Pat. Nos. 3,221,056and 3,419,614.

U.S. Pat. No. 4,191,659 describes the preparation of sulfurized olefiniccompounds by the catalytic reaction of sulfur and hydrogen sulfide witholefinic compounds containing from 3 to 30 carbon atoms. Such compoundsare reported to being useful in lubricating compositions, particularlythose prepared for use as industrial gear lubricants. U.S. Pat. No.4,119,549 describes a similar procedure for sulfurizing olefinsutilizing sulfur and hydrogen sulfide following by removal of lowboiling materials from said sulfurized mixture.

Other sulfurized compositions of matter also have been suggested ascompositions useful as additives for lubricants. U.S. Pat. No. 2,012,446describes a method of sulfurizing pine oil which is reported as beinguseful as an additive for lubricant manufacture. U.S. Pat. No. 3,953,347describes a sulfurized composition matter which is prepared by reactingsulfur with a mixture of at least one fatty acid ester of a polyhydricalcohol, at least one fatty acid and at least one aliphaticalpha-olefin. These latter compositions are suitable as replacement forsulfurized sperm oil as extreme pressure additives in lubricants.

SUMMARY OF THE INVENTION

A sulfurized composition prepared by sulfurizing a mixture of at leastone terpene and at least one other olefinic compound is described. Moreparticularly, sulfurized compositions prepared by sulfurizing a mixtureof pine oil and at least one other olefinic compound are described. Suchsulfurized compositions are useful as additive compositions inindustrial and gear lubricants, and more particularly, as lubricantadditive compositions. The compositions when added to lubricants providelubricants which exhibit improved antioxidant characteristics, nitrileseal compatibility and acceptable color characteristics.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

The sulfurized compositions of the present invention are prepared by theprocess which comprises sulfurizing a mixture comprising

(A) at least one terpene compound, and

(B) at least one other olefinic compound.

The term "terpene compound" as used in the specification and claims isintended to include the various isomeric terpene hydrocarbons having theempirical formula C₁₀ H₁₆, such as contained in turpentine, pine oil anddipentenes, and the various synthetic and naturally occuringoxygen-containing derivatives. Mixtures of these various compoundsgenerally will be utilized, especially when natural products such aspine oil and turpentine are used. Pine oil, for example, which isobtained by destructive distillation of waste pine wood withsuper-heated steam comprises a mixture of terpene derivatives such asalpha-terpineol, beta-terpineol, alpha-fenchol, camphor,borneol/isoborneol, fenchone, estragole, dihydro alpha-terpineol,anethole, and other mono-terpene hydrocarbons. The specific ratios andamounts of the various components in a given pine oil will depend uponthe particular source and the degree of purification. A group of pineoil-derived products are available commercially from HerculesIncorported. It has been found that the pine oil products generallyknown as terpene alcohols available from Hercules Incorporated areparticularly useful in the preparation of the sulfurized products of theinvention. Examples of such products include alpha-Terpineol containingabout 95-97% of alpha-terpineol, a high purity tertiary terpene alcoholmixture typically containing 96.3% of tertiary alcohols; Terpineol 318Prime which is a mixture of isomeric terpineols obtained by dehydrationof terpene hydrate and contains about 60-65 weight percent ofalpha-terpineol and 15-20% beta-terpineol, and 18-20% of other tertiaryterpene alcohols. Other mixtures and grades of useful pine oil productsalso are available from Hercules under such designations as Yarmor 302,Herco pine oil, Yarmor 302W, Yarmor F and Yarmor 60.

The terpene compounds which can be utilized in the preparation of thesulfurized compositions of the present invention also may be sulfurizedterpene compounds, sulfurized mixtures of terpene compounds or mixturesof at least one terpene compound and at least one sulfurized terpenecompound. Sulfurized terpene compounds can be prepared by sulfurizingterpene compounds with sulfur, sulfur halides, or mixtures of sulfur orsulfur dioxide with hydrogen sulfide as will be described more fullyhereinafter. Also, the sulfurization of various terpene compounds hasbeen described in the prior art. For example, the sulfurization of pineoil is described in U.S. Pat. No. 2,012,446.

Component (B) which is included in the mixture to be sulfurized inaccordance with the method of the invention is at least one otherolefinic compound. The olefinic compounds contain at least one olefinicdouble bond which is defined as a non-aromatic double bond. That is, thedouble bond connects two aliphatic carbon atoms. In its broadest sense,the olefin utilized as component (B) may be defined by the formula

    R.sup.1 R.sup.2 C═CR.sup.3 R.sup.4

wherein

each of R¹, R², R³ and R⁴ is hydrogen or an organic group. In general,the R values in the above formula which are not hydrogen may besatisfied by such groups as --R⁵, --C(R⁵)₃, --COOR⁵, --CON(R⁵)₂,--COON(R⁵)₄, --COOM, --CN, ##STR1## wherein: each R⁵ is independentlyhydrogen, alkyl, alkenyl, aryl, alkylaryl, substituted alkyl orsubstituted alkenyl, with the proviso that any two R⁵ groups can bealkylene or substituted alkylene whereby a ring of up to about 12 carbonatoms is formed;

M is one equivalent of a metal cation (preferably Group I or II, e.g.,sodium, potassium, barium, calcium);

X is halogen (e.g., chloro, bromo, or iodo); and

Y is oxygen or divalent sulfur.

Any two of R¹, R², R³ and R⁴ may also together form an alkylene orsubstituted alkylene group; i.e., the olefinic compound may bealicyclic.

The nature of the substituents in the substituted moieties describedabove is not normally a critical aspect of the invention and any suchsubstituent is useful so long as it is or can be made compatible withlubricating environments and does not interfere under the contemplatedreaction conditions. Thus, substituted compounds which are so unstableas to deleteriously decompose under the reaction conditions employed arenot contemplated. However, certain substituents such as keto or aldehydocan desirably undergo sulfurization. The selection of suitablesubstituents is within the skill of the art or may be establishedthrough routine testing. Typical of such substituents include any of theabove-listed moieties as well as hydroxy, carboxy, carbalkoxy, amidine,amino, sulfonyl, sulfinyl, sulfonate, nitro, phosphate, phosphite,alkali metal mercapto and the like.

The olefinic compound is usually one in which each R group which is nothydrogen is independently alkyl or alkenyl, or (less often) acorresponding substituted group. Monoolefinic and diolefinic compounds,particularly the former, are preferred, and especially terminalmonoolefinic hydrocarbons; that is, those compounds in which R³ and R⁴are hydrogen and R¹ and R² are alkyl (that is, the olefin is aliphatic).Olefinic compounds having at least about 3 carbon atoms, and especiallyabout 3 to about 36 carbon atoms are desirable. Olefins containing fromabout 8 to 24 carbon atoms are particularly useful.

The olefinic compound also can be an arylaliphatic compound,particularly wherein the aryl group is a phenyl or substituted phenylgroup. Specific examples include styrene, alpha-methyl styrene, vinyltoluene, 4-ethyl vinyl benzene, etc.

Propylene, isobutene and their dimers, trimers, tetramers and oligomers,and mixtures thereof are especially preferred olefinic compounds.Examples of useful olefins include isobutene, 1-butene, 1-hexene,1-octene, diisobutene, cyclohexene, triisobutene, commercially availablehigher aliphatic alpha-olefins, especially those in the C₁₂₋₃₀ range,such as 1-hexadecene and 1-octadecene, and commercial mixtures thereofsuch as C₁₅₋₂₀ alpha-olefins, C₁₆ alpha-olefins, C₁₅₋₁₈ alpha-olefins,C₂₂₋₂₈ alpha-olefins, etc.

Polymers of olefins such as, for example, isobutene also are useful solong as they and their sulfurized derivatives are compatible with theother components, and the sulfurized product does not lose its desirableproperties. Polybutenes having number average molecular weights of up toabout 1000 or 1500 are examples of useful polyolefins.

Generally, the olefinic component (B) is at least one aliphatic, arylaliphatic, or alicyclic olefinic compound containing at least about 3carbon atoms. Such olefinic compounds containing from about 3 to about36 carbon atoms and more preferably from about 8 to about 24 carbonatoms are particularly useful. It is common to use mixtures of sucholefins as component (B) since these mixtures are availablecommercially.

Component (B) also may be an unsaturated fatty acid, an unsaturatedfatty acid ester, mixtures thereof, or mixtures thereof with the olefinsdescribed above. The term "fatty acid" as used herein refers to acidswhich may be obtained by hydrolysis of naturally occurring vegetable oranimal fats or oils. These fatty acids usually contain from 16 to 20carbon atoms and are mixtures of saturated and unsaturated fatty acids.The unsaturated fatty acids generally contained in the naturallyoccurring vegetable or animal fats and oils may contain one or moredouble bonds and such acids include palmitoleic acid, oleic acid,linoleic acid, linolenic acid, and erucic acid.

The unsaturated fatty acids useful as component (B) may comprisemixtures of acids such as those obtained from naturally occurring animaland vegetable oils such as lard oil, tall oil, peanut oil, soybean oil,cottonseed oil, sunflower seed oil, or wheat germ oil. Tall oil is amixture of rosin acids, mainly abietic acid, and unsaturated fattyacids, mainly oleic and linoleic acids. Tall oil is a by-product of thesulfate process for the manufacture of wood pulp.

The most particularly preferred unsaturated fatty acid esters useful inthis invention are the fatty oils, that is, naturally occurring estersof glycerol with the fatty acids described above, and synthetic estersof similar structure. Examples of naturally occurring fats and oilscontaining unsaturation include animal fats such as Neat's-foot oil,lard oil, depot fat, beef tallow, etc. Examples of naturally occurringvegetable oils useful as component (B) include cottonseed oil, corn oil,poppy-seed oil, safflower oil, sesame oil, soybean oil, sunflower seedoil and wheat germ oil.

The fatty acid esters which are useful as component (B) in the inventionalso may be prepared from aliphatic olefinic acids of the type describedabove such as oleic acid, linoleic acid, linolenic acid, and behenicacid by reaction with alcohols and polyols. Examples of aliphaticalcohols which may be reacted with the above-identified acids includemonohydric alcohols such as methanol, ethanol, n-propanol, isopropanol,the butanols, etc.; and polyhydric alcohols including ethylene glycol,propylene glycol, trimethylene glycol, neopentyl glycol, glycerol, etc.

The other olefinic compound utilized component (B) in the preparation ofthe compositions of the invention includes sulfurized derivatives ofsaid olefinic compounds. Thus, component (B) may be any one or more ofthe above-identified olefinic compound, their sulfurized derivatives, ormixtures of said olefinic compounds and sulfurized derivatives. Thesulfurized derivatives can be prepared by methods known in the artutilizing sulfurizing reagents such as sulfur, sulfur halides ormixtures of sulfur or sulfur dioxide with hydrogen sulfide.

The amounts of the terpene compounds (A) and other olefinic compounds(B) contained in the mixture to be sulfurized can vary over a wide rangealthough it is essential that when the sulfurized compositions of thepresent invention are intended to be utilized as lubricant additives, asufficient amount of the other olefinic compounds should be contained inthe mixture to result in a sulfurized composition having the desiredoil-solubility. It has been observed that sulfurized terpenes such assulfurized pine oil generally do not exhibit the desired oil solubilitycharacteristics, and it is essential that the mixture to be sulfurizedcontain enough of the other olefinic compound to result in the formationof a sulfurized composition having the desired oil-solubility.Generally, the equivalent ratio of component (A) to component (B) isfrom about 1:20 to about 10:1, and more generally will range from about1:10 to about 5:1. More preferably, the equivalent ratio of component(A) to component (B) will be from about 1:10 to about 2:1. As mentionedabove, the other olefinic compound, component (B) may be (i) at leastone aliphatic, aryl aliphatic or alicyclic olefinic hydrocarboncontaining at least 3 carbon atoms, (ii) at least one unsaturated fattyacid or unsaturated fatty acid ester, (iii) at least one sulfurizedderivative of (i) or (ii), and (iv) mixtures thereof. The equivalentratios of the various olefinic compounds when mixtures are utilized canbe varied over a wide range, and the particular equivalent ratios willdepend upon the raw materials available as well as the propertiesdesired in the sulfurized composition.

It is frequently advantageous to incorporate materials useful assulfurization promoters in the reaction mixture. These materials may beacidic, basic or neutral. Useful neutral and acidic materials includeacidified clays such as "Super Filtrol", p-toluenesulfonic acid,phosphorus-containing reagents such as phosphorus acids (e.g.,dialkyl-phosphorodithioic acids, phosphorus acid esters (e.g., triphenylphosphate), phosphorus sulfides such as phosphorus pentasulfide andsurface active agents such as lecithin.

The preferred promoters are basic materials. These may be inorganicoxides and salts such as sodium hydroxide, calcium oxide and sodiumsulfide. The most desirable basic promoters, however, are nitrogen basesincluding ammonia and amines. The amines include primary, secondary andtertiary hydrocarbyl amines wherein the hydrocarbyl radicals are alkyl,aryl, aralkyl, alkaryl or the like and contain about 1 to 20 carbonatoms. Suitable amines include aniline, benzylamine, dibenzylamine,dodecylamine, naphthylamine, tallow amines, N-ethyldipropylamine,N-phenylbenzylamine, N,N-diethylbutylamine, m-toluidine and2,3-xylidine. Also useful are heterocyclic amines such as pyrrolidine,N-methylpyrrolidine, piperidine, pyridine and quinoline.

The preferred basic promoters include ammonia and primary, secondary, ortertiary alkylamines having about 1 to 8 carbon atoms in the alkylradicals. Representative amines of this type are methylamine,dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine,di-n-butylamine, tri-n-butylamine, tri-sec-hexylamine andtri-n-octylamine. Mixtures of these amines can be used as well asmixtures of ammonia and amines.

The amount of promoter material used is generally about 0.0005-2.0% ofthe combined weight of the terpene and olefinic compounds. In the caseof the preferred ammonia and amine catalysts, about 0.0005-0.5 mole permole of the combined weight is preferred, and about 0.001-0.1 mole isespecially desirable.

Water is also present in the reaction mixture either as a promoter or asa diluent for one or more of the promoters recited hereinabove. Theamount of water, when present, is usually about 1-25% by weight of theolefinic compound. The presence of water is, however, not essential andwhen certain types of reaction equipment are used it may be advantageousto conduct the reaction under substantially anhydrous conditions.

When promoters are incorporated into the reaction mixture as describedhereinabove, it is generally observed when a promoter is used is thatthe reaction can be conducted at lower temperatures, and the productgenerally is lighter in color.

The sulfurizing reagent used in this invention may be, for example,sulfur, a sulfur halide such as sulfur monochloride or sulfurdichloride, a mixture of hydrogen sulfide and sulfur or sulfur dioxide,or the like. Sulfur, or mixtures of sulfur and hydrogen sulfide oftenare preferred. However, it will be understood that other sulfurizationreagents may, when appropriate, be substituted therefor. Commercialsources of all the sulfurizing reagents are normally used for thepurpose of this invention, and impurities normally associated with thesecommercial products may be present without adverse results.

When the sulfurization reaction is effected by the use of sulfur alone,the reaction is effected by merely heating the reagents with the sulfurat temperatures of from about 50° to 250° C., usually, from about 150°to about 210° C. The weight ratio of the combination of components (A)and (B) to sulfur is between about 5:1 and about 15:1, generally betweenabout 5:1 and about 10:1. The sulfurization reaction is conducted withefficient agitation and generally in an inert atmosphere (e.g.,nitrogen). If any of the components or reagents are appreciably volatileat the reaction temperature, the reaction vessel may be sealed andmaintained under pressure. It is frequently advantageous to add thesulfur portionwise to the mixture of the other components.

When mixtures of sulfur and hydrogen sulfide are utilized in the processof the invention, the amounts of sulfur and hydrogen sulfide per mole ofcomponents (A) and (B) are, respectively, usually about 0.3 to about 3gram-atoms and about 0.1 to about 1.5 moles. A preferred range is fromabout 0.5 to about 2.0 gram-atoms and about 0.4 to about 1.25 moles,respectively, and the most desirable ranges are about 0.8 to about 1.8gram-atoms, and about 0.4 to about 0.8 mole, respectively. In batchoperations, the components are introduced at levels to provide theseranges. In semi-continuous operations, they may be admixed at any ratio,but on a mass balance basis, they are present so as to be consumed inamounts within these ratios. Thus, for example, if the reaction vesselis initially charged with sulfur alone, the olefinic compound andhydrogen sulfide are added incrementally at a rate such that the desiredratio is obtained.

When mixtures of sulfur and hydrogen sulfide are utilized in thesulfurization reaction, the temperature range of the sulfurizationreaction is generally from about 50° to about 350° C. The preferredrange is about 100° to about 200° C. with about 120° to about 180° C.being especially suitable. The reaction often is conducted under superatmospheric pressure which may be and usually is autogenous pressure(i.e., pressure which naturally developed during the course of thereaction), but may also be externally applied pressure. The exactpressure developed during the reaction is dependent upon such factors asdesign and operation of the system, the reaction temperature, and thevapor pressure of the reactants and products, and it may vary during thecourse of the reaction.

As a preferred procedure the sulfurized composition is prepared by theprocess which comprises the steps of:

(A) preparing a mixture comprising sulfur and at least one terpenecompound,

(B) heating said mixture to a temperature of up to about 150° C. andmaintaining this temperature for a period of from about 2 to 20 hours,

(C) raising the temperature of the mixture to up to about 200° C. whileremoving water and volatile materials,

(D) adding at least one aliphatic olefinic compound to the mixture andmaintaining the mixture at a temperature up to about 200° C. for aperiod of up to about 15 hours.

While it is preferred generally that the reaction mixture consistsentirely of the components and reagents described above, the reactionalso may be effected in the presence of an inert solvent (e.g., analcohol, ether, ester, aliphatic hydrocarbon, halogenated aromatichydrocarbon, etc.) which is liquid within the temperature rangeemployed. When the reaction temperature is relatively high, for example,at about 200° C., there may be some evolution of sulfur from the productwhich is avoided is a lower reaction temperature such as from about150°-170° C. is used.

The sulfurization of components (A) and (B) can be carried outsequentially in steps or all in one step simultaneously. The order ofthe sulfurization of components (A) and (B) is not critical to theinvention. Accordingly, a mixture of components (A) and (B) can beprepared and then sulfurized. In another embodiment, the terpenecomponent (A) is sulfurized in accordance with the process of theinvention, and thereafter, the other olefinic compound is added to themixture and the mixture is heated to an elevated temperature to effectthe sulfurization of the olefin. In another embodiment, the olefiniccompound (B) is first sulfurized, and the terpene compound (A) is thenadded and sulfurized with or without additional sulfur. In yet anotherembodiment, terpene compound (A) is sulfurized, and to the sulfurizedterpene compound, there is added a separately prepared sulfurizedolefinic compound (B), and this mixture is heated with or without addingadditional sulfur to effect a further sulfurization of the mixture.

The time required for the sulfurization reaction to be completed willvary depending the upon the reagents, the ratios thereof, the reactiontemperature, the presence or absence of promoters, and the purity of thereagents. When a mixture of sulfur and sulfur dioxide is used as thesulfurizing agent and the reaction is conducted at an elevated pressurein a closed vessel, the course of the reaction can conveniently befollowed by monitoring the pressure in the reaction vessel. The reactiongenerally can be considered complete when the pressure levels off to aconstant value. Following the preparation of the sulfurized mixture bythe procedures described above, it is generally preferred to removesubstantially all low boiling materials, typically by venting thereaction vessel or by distillation at atmospheric pressure, vacuumdistillation or stripping, or the passage of an inert gas such asnitrogen through the mixture at a suitable temperature and pressure. Anysolids which are present in the reaction mixture may be removedconveniently, in most instances, by merely pouring off the liquidproduct. If further removal of solids is desired, such conventionaltechniques as filtration or centrifugation may be used.

In some instances, it may be desirable to treat the sulfurized productobtained in accordance with the procedures described herein to reduceactive sulfur. The term "active sulfur" includes sulfur in a form whichcan cause staining of copper and similar materials, and standard testsare available to determine sulfur activity. As an alternative to thetreatment to reduce active sulfur, metal deactivators can be used andthe lubricants containing sulfurized compositions of this invention. Insome instances, such as in metal working lubricants, high levels ofactive sulfur may be desired, and in those situations, it may bepreferred not to reduce active sulfur.

When active sulfur is to be reduced, several methods known in the artmay be employed and an illustrative method utilizing an alkali metalsulfide is described in U.S. Pat. No. 3,498,915. Other optionaltreatments may be employed to remove such qualities such as the odor,color and staining characteristics of the sulfurized compositions of theinvention. These may include treatment with acidic clays such as SuperFiltrol, activated charcoal, aluminum clays, etc.

The exact chemical nature of the sulfurized compositions of thisinvention is not known with certainty, and it is most convenient todescribe them in terms of their method of preparation. The sulfurcontent of the sulfurized compositions of the invention can vary over awide range, although the sulfurized compositions of the presentinvention generally will contain up to about 35 to 40% sulfur, and moregenerally from about 15 to 30 or 35% by weight of sulfur.

The compositions of this invention generally will be derived frommixtures wherein components (A) and (B) are present in equivalent ratiosof from about 1:20 to about 10:1, and more preferably, from about 1:10to about 5:1 or 2:1.

The following examples illustrate the preparation of sulfurized terpenecompounds and sulfurized olefinic compounds which are useful ascomponents (A) and (B) respectively in the present invention. Unlessotherwise indicated, all parts and percentages are by weight, andtemperatures are in degrees centigrade.

EXAMPLE A

To a reaction vessel there is charged 372 parts (2 equivalents) of acommercially available pine oil (Sargent Welch), and the pine oil isheated and stirred. Sulfur (128 parts) is added slowly with nitrogenblowing while the reaction temperature is maintained at about 35° C.After addition of the sulfur is completed, nitrogen is bubbled throughthe reaction mixture while it is heated to reflux at about 145° C. Aftera total reaction time of about 8 hours, the mixture is filtered throughfilter aid. The filtrate is the desired sulfurized product containing23.35% sulfur (theory 25.6).

EXAMPLE B

The procedure of Example A is repeated except that the reaction mixturecomprises 186 parts of pine oil (1 equivalent) and 32 parts of sulfur(1.0 equivalent). The product obtained in this matter has a sulfurcontent of 15.6% (theory 14.68).

EXAMPLE C

To a reaction vessel there is added 372 parts (2 equivalents) of pineoil and 96 parts (3 equivalents) of sulfur. When all of the sulfur isadded, the mixture is heated to 150° C. with nitrogen blowing, and themixture is maintained at this temperature for about 10 hours. Thereaction mixture is filtered through a filter aid, and the filtrate isthe desired product having a sulfur content of 17.25% (theory 20.5).

EXAMPLE D

Pine oil (372 parts, 2 equivalents) is added to a reaction vessel, andthe pine oil is heated with stirring. Sulfur (190 parts, 6 equivalents)is added slowly to the stirred pine oil, and after addition iscompleted, nitrogen is blown through the reaction mixture which isheated to a temperature of about 145° C. Triethanol amine (5.62 parts)is added, and heating of the mixture is continued with reflux until thesulfur appears to be dissolved. The mixture is filtered, and thefiltrate is the desired product containing 25.4% sulfur (theory 33.80).

EXAMPLE E

Sulfur (526 parts, 16.4 moles) is charged to a jacketed high pressurereactor which is fitted with an agitator and internal cooling coils.Refrigerated brine is circulated through the coils to cool the reactorprior to the introduction of the gaseous reactants. After sealing thereactor, evacuating to about 2 torr and cooling, 920 parts (16.4 moles)of isobutene and 279 parts (8.2 moles) of hydrogen sulfide are chargedto the reactor. The reactor is heated using steam in the externaljacket, to a temperature of about 182° C. (360° F.) over about 1.5hours. A maximum pressure of 1350 psig. is reached at about 168° C.(335° F.) during this heat-up. Prior to reaching the peak reactiontemperature, the pressure starts to decrease and continues to decreasesteadily as the gaseous reactants are consumed. After about 10 hours ata reaction temperature of about 182° C., the pressure is 310-340 psig.and the rate of pressure change is about 5-10 psig. per hour. Theunreacted hydrogen sulfide and isobutene are vented to a recoverysystem. After the pressure in the reactor has decreased to atmospheric,the sulfurized mixture is recovered as a liquid.

The mixture is blown with nitrogen at about 100° C. (212° F.) to removelow boiling materials including unreacted isobutene, mercaptans andmonosulfides. The residue after nitrogen blowing is agitated with 5%Super Filtrol and filtered, using a diatomaceous earth filter aid. Thefiltrate is the desired sulfurized composition which contains 42.5%sulfur.

EXAMPLE F

The procedure of Example E is repeated except that the isobutylene isreplaced by a C₁₆ -C₁₈ alpha-olefin, the molar ratio of olefin:sulfur:H₂S is 1:1.5:0.5, and the reaction temperature is about 171° C. Theproduct obtained from this example contains 20.6% sulfur.

EXAMPLE G

The procedure of Example E is repeated except that the isobutene isreplaced by a polyisobutene having a number average molecular weight ofabout 1000 as determined by vapor pressure osmometry. The ratio ofpolyisobutene:sulfur:H₂ S is 1:0.5:0.5, and the reaction temperature is171° C. The sulfurized product obtained in this manner contains about2.6% sulfur.

The following examples illustrate the preparation of the sulfurizedcompositions of the present invention.

EXAMPLE H

A mixture of 60 parts of commercial C₁₅₋₂₀ alpha-olefins and 100 partsof lard oil is heated to 160° C. under nitrogen, and 12 parts of sulfurare added. The mixture is heated at 165°-200° C., and an additional 6.5parts of sulfur are added. Heating is continued for four hours afterwhich the mixture is cooled to 100° C. and filtered. The filtrate is thedesired product which contains 9.0% sulfur.

EXAMPLE I

A mixture of 100 parts of soybean oil and 50 parts of commercial C₁₆alpha-olefins is heated to 175° C. under nitrogen, and 17.4 parts ofsulfur are added gradually whereupon an exothermic reaction causes thetemperature to rise to 205° C. The temperature is maintained at about188°-200° C. for about 5 hours, allowed to cool gradually to 90° C. andfiltered to yield the desired product containing 10.13% sulfur.

EXAMPLE 1

A mixture of 111 parts (0.5 mole) of a distilled C₁₆ alpha-olefin and 93parts (0.5 mole) of pine oil is prepared and heated with stirring in areaction vessel. Sulfur (64 parts, 2 moles) is added slowly, and thereaction temperature is raised to about 170° C. The reaction mixture ismaintained at a temperature of 160° C. with nitrogen blowing. Somerefluxing of the light ends of the pine oil is observed. The reactionmixture is then cooled and filtered through a filter aid. The filtrateis the desired product containing 25.16% sulfur (theory 23.9).

EXAMPLES 2-5

The general procedure of Example 1 is repeated except that theequivalent ratio of olefin:pine oil:sulfur is varied, and in Example 5,a promoter system consisting of 0.043 equivalent of triethanol amine and0.01 equivalent of 2,5-bis(tertoctyldithio) thiadiazole are used aspromoter for each equivalent of pine oil and the mixture. Furtherdetails regarding these examples is found in the following Table I.

                  TABLE I    ______________________________________                      Equivalent Ratio                                    % S in Product    Example           Olefin     Olefin/Pine Oil/S                                    Act/Theory    ______________________________________    2      C.sub.16 olefin                      1:1:3         19.07/19.09    3      C.sub.16 olefin                      1:1:5         27.44/28.17    4      C.sub.16 olefin                      1:1:6         28.82/32    5      C.sub.16 olefin                      1:1:5         24.57/27.77    ______________________________________

EXAMPLE 6

A mixture of 186 parts (1 equivalent) of pine oil and 168 parts (1equivalent) of polypropylene is prepared, and 96 parts (3 equivalents)of sulfur are added with stirring. The reaction mixture is heated to atemperature of about 170° C. with nitrogen blowing and maintained atthis temperature for 10 hours. The reaction mixture then is cooled andfiltered through filter aid. The filtrate is the desired product havinga sulfur content of 16.79% (theory 21.33%).

EXAMPLE 7

The procedure of Example 6 is repeated except that the equivalent ratioof polypropylene:pine oil:sulfur is 1:1:4, and the reaction mixture ismaintained at 170° C. for about 8 hours. The product obtained in thismanner contains 27.30% sulfur (theory 26.55).

EXAMPLE 8

The mixture of 186 parts of pine oil (1 equivalent), 126 parts of nonene(1 equivalent) and 192 parts (6 equivalents) of sulfur is prepared andheated to reflux at about 135° C. for 2 hours. After cooling overnight,10.1 parts of triethyl amine (0.1 equivalent) and 4.3 parts of2,5-bis(tert-octyldithio) thiadiazole are added as promoter. The mixtureis heated to 135°-140° C. with nitrogen blowing until the reactionmixture becomes clear. The mixture is heated an additional 6 hours atreflux and filtered through a filter aid. The filtrate is the desiredproduct containing 33.49% sulfur (theory 37.1%).

EXAMPLE 9

Polypropylene (252 parts, 1.5 equivalents) is charged to a reactionvessel equipped with a condenser and stirrer. The polypropylene isstirred and 48 parts (1.5 equivalents) of sulfur are added. Thisreaction mixture is heated to about 170° C. and maintained at thistemperature for about 5 hours and cooled. Pine oil (279 parts, 1.5equivalents) is added to the reaction mixture which is then heated to atemperature of about 150° C. and maintained at this temperature withnitrogen blowing for about 8 hours. The mixture is cooled and filteredthrough a filter aid to yield the desired product having a sulfurcontent of 8.36% (theory 8.2%).

EXAMPLE 10

Polypropylene (336 parts, 2 equivalents) is charged to a reaction vesselequipped with condenser, thermometer and stirrer. The mixture is heated,and 128 parts (4 equivalents) of sulfur are added, and the temperatureis slowly increased to about 170° C. with nitrogen blowing. The reactionmixture is maintained at a temperature of about 160°-170° C. for about 8hours, and after cooling to a temperature of about 70° C., 372 parts (2equivalents) of pine oil are added, and the mixture is reheated to about130° C. After cooling the mixture to add a foam trap, it is reheated toa temperature of 140°-150° C. and maintained at this temperature forabout 4 hours. The mixture is cooled to about 35° C. and filteredthrough a filter aid. The filtrate is the desired product having asulfur content of about 15.1% (theory 15.31%).

EXAMPLE 11

A mixture of 93 parts (0.5 equivalent) of pine oil and 48 parts (1.5equivalents) of sulfur is charged to a reaction vessel equipped withcondenser, thermometer and stirrer. The mixture is heated to about 140°C. with nitrogen blowing and maintained at this temperature for about 28hours. After cooling, 111 parts of a C₁₆ alpha-olefin (available fromGulf Oil Chemicals Company under the general trade name Gulftene 16) areadded through an addition funnel, and after addition is complete, theaddition funnel is replaced with a nitrogen tube. The reaction mixtureis heated to 170° C. with nitrogen blowing and maintained at thetemperature for about 5 hours. The mixture is cooled and filteredthrough a filter aid. The filtrate is the desired product having asulfur content of 19.01% (theory 19.04%).

EXAMPLE 12

A mixture of 372 parts (2 equivalents) of pine oil and 544 parts (17equivalents) of sulfur is prepared and heated to a temperature of about140°-145° C. and maintained at this temperature for 8 hours. A C₁₆alpha-olefin (444 parts, 2 equivalents) is added and this reactionmixture is heated to 180°-185° C. while removing water and light ends.The mixture is filtered, and the filtrate is the desired productcontaining 30.9% sulfur (theory 40%).

EXAMPLE 13

A mixture of 372 parts (2 equivalents) of pine oil and 397 parts (12.4equivalents) of sulfur is prepared and heated with stirring and nitrogenblowing to a temperature of about 140°-145° C. The mixture is maintainedat this temperature for about 8 hours whereupon 222 parts (1 equivalent)of a C₁₆ alpha-olefin are added. This mixture is heated to about 180° C.and maintained at this temperature for about 5 hours and is filteredafter cooling to about 70° C. The filtrate is the desired product.

EXAMPLE 14

A mixture of 186 parts (1 equivalent) of pine oil and 420 parts (13.1equivalents) of sulfur is prepared and heated to a temperature of about140°-145° C. The mixture is maintained at this temperature for about 8hours, and 444 parts (2 equivalents) of a C₁₆ alpha-olefin are added.This mixture is heated to 180°-185° C. with nitrogen blowing whileremoving a small amount of light ends and water. The mixture is filteredthrough filter aid to give the desired product having a sulfur contentof 29.89%.

EXAMPLE 15

A mixture of 93 parts (0.5 equivalent) of pine oil and 90 parts (1.25equivalents) of sulfur is prepared and heated to 140° C. with nitrogenblowing. The temperature is maintained at about 140° C. for about 20hours whereupon 111 parts (0.5 equivalent) of a C₁₆ alpha-olefin areadded dropwise over a period of about one hour. The temperature isincreased to about 180° C. with nitrogen blowing, and the mixture ismaintained at this temperature for about 12 hours. The reaction mixtureis cooled and filtered to yield the desired product containing 15.4% ofsulfur (theory 16.4%).

EXAMPLE 16

A mixture of 372 parts (2 equivalents) of steam distilled pine oil(Sergeant-Welch) and 119 parts (3.72 mole equivalents) of sulfur isprepared and heated with nitrogen blowing to a temperature of 140° C.for about 8 hours. After to 100° C., 444 parts (2 equivalents) of a C₁₆alpha-olefin are added over a period of about one hour. The mixture thenis heated to about 180° C. and maintained at this temperature for about6 hours. After cooling to a temperature of about 100° C., the reactionmixture is filtered to yield the desired product containing 15.3% sulfur(theory 13.0%).

EXAMPLE 17

A mixture of 186 parts (1 equivalent) of steam distilled pine oil and 96parts (3 equivalents) of sulfur is heated to reflux and maintained atthis temperature with stirring and nitrogen blowing for about 4 hours.Lard oil (391 parts, 1 equivalent) is added and the mixture heated withstirring and nitrogen blowing for about 8 hours at 180° C. Twenty partsof water and 22 parts of light ends are removed during this period. Thereaction mixture is filtered through filter aid to yield the desiredproduct containing 12.45% sulfur (theory 14.3%).

EXAMPLE 18

A mixture of 186 parts (1 equivalent) of steam distilled pine oil and 96parts (3 equivalents) of sulfur is heated to 140° C. with nitrogenblowing for a period of about 4 hours while removing 4 parts of water.Lard oil (391 parts, 1 equivalent) is added followed by the addition of1.5 parts of phosphoric acid as a promoter. This mixture is heated to180° C. and maintained at this temperature for about 8 hours whileremoving additional water and about 20 parts of light ends. The mixtureis filtered through filter aid to yield the desired product containing14.14% of sulfur (theory 15.07%).

EXAMPLE 19

A mixture of 186 parts (1 equivalent) of steam distilled pine oil, 96parts (3 equivalents) of sulfur and 1.5 parts of phosphoric acidprepared and heated to a temperature of about 140° C. while stirring andwith nitrogen blowing. The mixture then is heated up to about 200° C.while collecting about 15 parts of water whereupon the mixture is cooledto 140° C. and held at this temperature for about 4 hours. Lard oil (391parts, 1 equivalent) is added and the mixture heated to 180° C. andmaintained at this temperature for about 8 hours while blowing withnitrogen. The reaction mixture is filtered through a filter aid to yieldthe desired product having a sulfur content of 21.59% (theory 15.3%).

EXAMPLE 20

A mixture of 159 parts (1 equivalent) of pine oil and 545 parts (1equivalent) of a polyisobutenyl substituted succinic anhydride isprepared and heated to a temperature of about 140° C. while removingsome of the light ends of the pine oil. The mixture then is heated toand maintained at a temperature of about 180° C. for about 6 hours.After cooling, 5.2 parts (0.13 equivalent) of ethyleneamine polyamineare added to the reaction vessel and this mixture is heated to 180° C.and maintained at this temperature for about 12 hours. After coolingovernight, 24 parts (0.75 equivalent) of sulfur is added and the mixtureis reheated to 180° C. The mixture is maintained at 180° C. for about 8hours and thereafter filtered through filter aid. The filtrate is thedesired product containing 2.63% sulfur (repeat 2.33%).

EXAMPLE 21

A mixture of 372 parts (2 equivalents) of Yarmor 60 pine oil availablefrom Hercules Incorporated and containing about 62.7% of terpenealcohols, and 192 parts (6 equivalents) of sulfur is prepared in areaction vessel equipped with a condenser, thermometer and stirrer. Themixture is heated with stirring and nitrogen blowing to a temperature ofabout 140° C. and maintained at this temperature for about 8 hours.Commercial C₁₆ alpha-olefin (444 parts, 2 equivalents) is added, and thetemperature of the mixture is increased to 170° C. and maintained atthis temperature for about 8 hours while removing 3 parts of water and27 parts of light ends. The reaction mixture is cooled to about 100° C.and filtered through a filter aid. The filtrate is the desired productcontaining 18.7% sulfur (theory 19.07%).

EXAMPLE 22

The procedure of Example 21 is repeated except that the pine oilutilized in this example is Yarmor F pine oil available from HerculesIncorporated and containing a total of about 75% of terpene alcohol. Theproduct obtained in this manner has a sulfur content of 18.4% (theory19.07%).

EXAMPLE 23

A mixture of 744 parts (4 equivalents) of steam distilled pine oil and384 parts (12 equivalents) of sulfur (8 mesh) is prepared and heated toa temperature of about 140°-145° C. and maintained at this temperaturefor about 8 hours. A water trap is then added to the reaction flaskwhereupon water and light ends are removed. Commercial C₁₆₁₈alpha-olefin (888 parts, 4 equivalents) is added dropwise over a periodof about 45 minutes while maintained at a reaction temperature at about180° C. for about 5 hours. The reaction mixture is cooled and filtered.The filtrate is the desired product containing 17.61% sulfur (theory20.0%).

EXAMPLE 24

A mixture of 100 parts of the product of Example A and about 125 partsof the product of Example E is prepared and heated to a temperature ofabout 200°-225° C. for 10 hours to yield the desired product uponfiltration.

EXAMPLE 25

The procedure of Example 24 is repeated except that 32 parts of sulfurare added to the mixture before the mixture is heated to a temperatureof about 200°-225° C.

EXAMPLE 26

The procedure of Example 24 is repeated except that the product ofExample E is replaced by an equivalent amount of the product of ExampleH.

EXAMPLE 27

The procedure of Example 26 is repeated except that 32 parts of sulfuris included in the mixture.

The sulfurized compositions of this invention are useful as additivesfor lubricants in which they function primarily as oxidation inhibitorsand extreme pressure and anti-wear agents. Lubricating oils containingthe sulfurized compositions of the invention exhibit good compatibilitywith synthetic elastomers such as those used as sealants in automotivetransmissions. Transmission fluid, for example, can affect the tensilestrength, elongation, hardness and volume of synthetic rubbers.Compounds such as Buna-N, polyacrylates and silicones are used intransmission oil seals. Lubricating compositions and automatictransmission fluids containing the sulfurized compositions of theinvention exhibit good nitrile seal compatibility. The sulfurizedproducts of the invention which include at least one terpene compoundexhibit improved oil-solubility when compared to sulfurized terpenes,and the presence of the terpene compound in the sulfurized mixturegenerally results in the production of sulfurized products characterizedby having a lighter color than can be obtained from the sulfurization ofolefins when terpenes are not present.

The sulfurized compositions of the invention can be effectively employedin a variety of lubricating compositions formulated for a variety ofuses. These lubricating compositions are based on diverse oils oflubricating viscosity, including natural and synthetic lubricating oilsand mixtures thereof. These lubricating compositions containing thesubject additive concentrates are effective as crankcase lubricatingoils for spark-ignited and compression-ignited internal combustionengines, including automobile and truck engines, two-cycle engines,aviation piston engines, marine and low-load diesel engines, and thelike. Also, automatic transmission fluids, transaxle lubricants, gearlubricants, metal-working lubricants, hydraulic fluids, and otherlubricating oil and grease compositions can benefit from theincorporation of the subject additive concentrates.

Natural oils include animal oils and vegetable oils (e.g., castor oil,lard oil) as well as mineral lubricating oils such as liquid petroleumoils and solvent-treated or acid-treated mineral lubricating oils of theparaffinic, naphthenic or mixed paraffinic-naphthenic types. Oils oflubricating viscosity derived from coal or shale are also useful.Synthetic lubricating oils include hydrocarbon oils and halosubstitutedhydrocarbon oils such as polymerized and interpolymerized olefins (e.g.,polybutylenes, polypropylenes, propyleneisobutylene copolymers,chlorinated polybutylenes, etc.); poly(1-hexenes), poly(1-octenes),poly(1-decenes), etc. and mixtures thereof; alkylbenzenes (e.g.,dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes,di-(2-ethylhexyl)-benzenes, etc.); polyphenyls (e.g., biphenyls,terphenyls, alkylated polyphenyls, etc.); alkylated diphenyl ethers andalkylated diphenyl sulfides and the derivatives, analogs and homologsthereof and the like.

Alkylene oxide polymers and interpolymers and derivatives thereof wherethe terminal hydroxyl groups have been modified by esterification,etherification, etc., constitute another class of known syntheticlubricating oils that can be used. These are exemplified by the oilsprepared through polymerization of ethylene oxide or propylene oxide,the alkyl and aryl ethers of these polyoxyalkylene polymers (e.g.,methylpolyisopropylene glycol ether having an average molecular weightof about 1000, diphenyl ether of polyethylene glycol having a molecularweight of about 500-1000, diethyl ether of polypropylene glycol having amolecular weight of about 1000-1500, etc.) or mono- and polycarboxylicesters thereof, for example, the acetic acid esters, mixed C₃ -C₈ fattyacid esters, or the C₁₃ Oxo acid diester of tetraethylene glycol.

Another suitable class of synthetic lubricating oils that can be usedcomprises the esters of dicarboxylic acids (e.g., phthalic acid,succinic acid, alkyl succinic acids, alkenyl succinic acids, maleicacid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipicacid, linoleic acid dimer, malonic acid, alkyl malonic acids, alkenylmalonic acids, etc.) with a variety of alcohols (e.g., butyl alcohol,hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol,diethylene glycol monoether, propylene glycol, etc.) Specific examplesof these esters include dibutyl adipate, di(2-ethylhexyl) sebacate,di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecylazelate, dioctyl phthalate, didecyl phthalate, dieicosyl sebacate, the2-ethylhexyl diester of linoleic acid dimer, the complex ester formed byreacting one mole of sebacic acid with two moles of tetraethylene glycoland two moles of 2-ethylhexanoic acid and the like.

Esters useful as synthetic oils also inlcude those made from C₅ to C₁₂monocarboxylic acids and polyols and polyol ethers such as neopentylglycol, trimethylol propane, pentaerythritol, dipentaerythritol,tripentaerythritol, etc.

Silicon-based oils such as the polyalkyl-, polyaryl-, polyalkoxy-, orpolyaryloxy-siloxane oils and silicate oils comprise another usefulclass of synthetic lubricants (e.g., tetraethyl silicate, tetraisopropylsilicate, tetra-(2-ethylhexyl)silicate, tetra-(4-methyl-hexyl)silicate,tetra-(p-tert-butylphenyl)silicate,hexyl-(4-methyl-2-pentoxy)disiloxane, poly(methyl)siloxanes,poly(methylphenyl)siloxanes, etc.). Other synthetic lubricating oilsinclude liquid esters of phosphorus-containing acids (e.g., tricresylphosphate, trioctyl phosphate, diethyl ester of decane phosphonic acid,etc.), polymeric tetrahydrofurans and the like.

Unrefined, refined and rerefined oils, either natural or synthetic (aswell as mixtures of two or more of any of these) of the type disclosedhereinabove can be used in the concentrates of the present invention.Unrefined oils are those obtained directly from a natural or syntheticsource without further purification treatment. For example, a shale oilobtained directly from retorting operations, a petroleum oil obtaineddirectly from primary distillation or ester oil obtained directly froman esterification process and used without further treatment would be anunrefined oil. Refined oils are similar to the unrefined oils exceptthey have been further treated in one or more purification steps toimprove one or more properties. Many such purification techniques areknown to those skilled in the art such as solvent extraction, secondarydistillation, acid or base extraction, filtration, percolation, etc.Rerefined oils are obtained by processes similar to those used to obtainrefined oils applied to refined oils which have been already used inservice. Such rerefined oils are also known as reclaimed or reprocessedoils and often are additionally processed by techniques directed toremoval of spent additives and oil breakdown products.

Generally the lubricants of the present invention contain an amount ofone or more of the sulfurized compositions of this invention sufficientto provide them with improved antioxidant, anti-wear and/or extremepressure properties. Normally the amount employed will be about 0.01% toabout 20%, preferably about 0.1% to about 10% of the total weight of thelubricating composition. This amount is exclusive of solvent/diluentmedium. In lubricating compositions operated under extremely adverseconditions, such as lubricating compositions for marine diesel engines,the compositions of this invention may be present in amounts of up toabout 30% by weight, or more, of the total weight of the lubricatingcomposition.

The invention also contemplates the use of other additives incombination with the sulfurized compositions of this invention. Suchadditives include, for example, detergents and dispersants of theash-producing or ashless type, corrosion- and oxidation-inhibitingagents, pour point depressing agents, extreme pressure agents, antiwearagents, color stabilizers and anti-foam agents.

The ash-producing detergents are exemplified by oil-soluble neutral andbasic salts of alkali or alkaline earth metals with sulfonic acids,carboxylic acids, or organic phosphorus acids characterized by at leastone direct carbon-to-phosphorus linkage such as those prepared by thetreatment of an olefin polymer (e.g., polyisobutene having a molecularweight of 1000) with a phosphorizing agent such as phosphorustrichloride, phosphorus heptasulfide, phosphorus pentasulfide,phosphorus trichloride and sulfur, white phosphorus and a sulfur halide,or phosphorothioic chloride. The most commonly used salts of such acidsare those of sodium, potassium, lithium, calcium, magnesium, strontiumand barium.

The term "basic salt" is used to designate metal salts wherein the metalis present in stoichiometrically larger amounts than the organic acidradical. The commonly employed methods for preparing the basic saltsinvolve heating a mineral oil solution of an acid with a stoichiometricexcess of a metal neutralizing agent such as the metal oxide, hydroxide,carbonate, bicarbonate, or sulfide at a temperature of about 50° C. andfiltering the resulting mass. The use of a "promoter" in theneutralization step to aid the incorporation of a large excess of metallikewise is known. Examples of compounds useful as the promoter includephenolic substances such as phenol, naphthol, alkylphenol, thiophenol,sulfurized alkylphenol, and condensation products of formaldehyde with aphenolic substance; alcohols such as methanol, 2-propanol, octylalcohol, cellosolve, carbitol, ethylene glycol, stearyl alcohol, andcyclohexyl alcohol; and amines such as aniline; phenylenediamine,phenothiazine; phenyl-beta-naphthylamine, and dodecylamine. Aparticularly effective method for preparing the basic salts comprisesmixing an acid with an excess of a basic alkaline earth metalneutralizing agent and at least one alcohol promoter, and carbonatingthe mixture at an elevated temperature such as 60°-200° C.

Ashless detergents and dispersants are so called despite the fact that,depending on its constitution, the dispersant may upon combustion yielda non-volatile material such as boric oxide or phosphorus pentoxide;however, it does not ordinarily contain metal and therefore does notyield a metal-containing ash on combustion. Many types are known in theart, and any of them are suitable for use in the lubricant compositionsof this invention. The following are illustrative:

(1) Reaction products of carboxylic acids (or derivatives thereof)containing at least about 34 and preferably at least about 54 carbonatoms with nitrogen containing compounds such as amine, organic hydroxycompounds such as phenols and alcohols, and/or basic inorganicmaterials. Examples of these "carboxylic dispersants" are described inBritish Pat. No. 1,306,529 and in many U.S. patents including thefollowing:

    ______________________________________    3,163,603  3,351,552        3,541,012    3,184,474  3,381,022        3,543,678    3,215,707  3,399,141        3,542,680    3,219,666  3,415,750        3,567,637    3,271,310  3,433,744        3,574,101    3,272,746  3,444,170        3,576,743    3,281,357  3,448,048        3,630,904    3,306,908  3,448,049        3,632,510    3,311,558  3,451,933        3,632,511    3,316,177  3,454,607        3,697,428    3,340,281  3,467,668        3,725,441    3,341,542  3,501,405        4,234,435    3,346,493  3,522,179        Re 26,433    ______________________________________

(2) Reaction products of relatively high molecular weight aliphatic oralicyclic halides with amines, preferably olyalkylene polyamines. Thesemay be characterized as "amine dispersants" and examples thereof aredescribed for example, in the following U.S. patents:

    ______________________________________           3,275,554                  3,454,555           3,438,757                  3,565,804    ______________________________________

(3) Reaction products of alkyl phenols in which the alkyl group containsat least about 30 carbon atoms with aldehydes (especially formaldehyde)and amines (especially polyalkylene polyamines), which may becharacterized as "Mannich dispersants". The materials described in thefollowing U.S. patents are illustrative:

    ______________________________________    2,459,112      3,442,808                            3,591,598    2,962,442      3,448,047                            3,600,372    2,984,550      3,454,497                            3,634,515    3,036,003      3,459,661                            3,649,229    3,166,516      3,461,172                            3,697,574    3,236,770      3,493,520                            3,725,277    3,355,270      3,539,633                            3,725,480    3,368,972      3,558,743                            3,726,882    3,413,347      3,586,629                            3,980,569    ______________________________________

(4) Products obtained by post-treating the carboxylic, amine or Mannichdispersants with such reagents as urea, thiourea, carbon disulfide,aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinicanhydrides, nitriles, epoxides, boron compounds, phosphorus compounds orthe like. Exemplary materials of this kind are described in thefollowing U.S. patents:

    ______________________________________    3,036,003             3,282,955     3,493,520                                    3,639,242    3,087,936             3,312,619     3,502,677                                    3,649,229    3,200,107             3,366,569     3,513,093                                    3,649,659    3,216,936             3,367,943     3,533,945                                    3,658,836    3,254,025             3,373,111     3,539,633                                    3,697,574    3,256,185             3,403,102     3,573,010                                    3,702,757    3,278,550             3,442,808     3,579,450                                    3,703,536    3,280,234             3,455,831     3,591,598                                    3,704,308    3,281,428             3,455,832     3,600,372                                    3,708,422    ______________________________________

(5) Interpolymers of oil-solubilizing monomers such as decylmethacrylate, vinyl decyl ether and high molecular weight olefins withmonomers containing polar substituents, e.g., aminoalkyl acrylates oracrylamides and poly-(oxyethylene)-substituted acrylates. These may becharacterized as "polymeric dispersants" and examples thereof aredisclosed in the following U.S. patents:

    ______________________________________           3,329,658                  3,666,730           3,449,250                  3,687,849           3,519,565                  3,702,300    ______________________________________

The above-noted patents are incorporated by reference herein for theirdisclosures of ashless dispersants.

Auxiliary extreme pressure agents and corrosion- andoxidation-inhibiting agents which may be included in the lubricants ofthe invention are exemplified by chlorinated aliphatic hydrocarbons suchas chlorinated wax; organic sulfides and polysulfides such as benzyldisulfide, bis(chlorobenzyl)disulfide, dibutyl tetrasulfide, sulfurizedmethyl ester of oleic acid, sulfurized alkylphenol, sulfurizeddipentene, and sulfurized terpene; phosphosulfurized hydrocarbons suchas the reaction product of a phosphorus sulfide with turpentine ormethyl oleate, phosphorus esters including principally dihydrocarbon andtrihydrocarbon phosphites such as dibutyl phosphite, diheptyl phosphite,dicyclohexyl phosphite, pentylphenyl phosphite, dipentylphenylphosphite, tridecyl phosphite, distearyl phosphite, dimethyl naphthylphosphite, oleyl 4-pentylphenyl phosphite, polypropylene (molecularweight 500)-substituted phenyl phosphite, diisobutyl-substituted phenylphosphite; metal thiocarbamates, such as zinc dioctyldithiocarbamate,and barium heptylphenyl dithiocarbamate; Group II metalphosphorodithioates such as zinc dicyclohexylphosphorodithioate, zincdioctylphosphorodithioate, barium di(heptylphenyl)phosphorodithioate,cadmium dinonylphosphorodithioate, and the zinc salt of aphosphorodithioic acid produced by the reaction of phosphoruspentasulfide with an equimolar mixture of isopropyl alcohol and n-hexylalcohol.

Many of the above-mentioned auxiliary extreme pressure agents andcorrosion-oxidation inhibitors also serve as antiwear agents. Zincdialkylphosphorodithioates are a well known example.

Pour point depressants are a particularly useful type of additive oftenincluded in the lubricating oils described herein. The use of such pourpoint depressants in oil-based compositions to improve low temperatureproperties of oil-based compositions is well known in the art. See, forexample, page 8 of "Lubricant Additives" by C. V. Smalheer and R.Kennedy Smith (Lezius-Hiles Co. publishers, Cleveland, Ohio, 1967).

Examples of useful pour point depressants are polymethacrylates;polyacrylates; polyacrylamides; condensation products of haloparaffinwaxes and aromatic compounds; vinyl carboxylate polymers; andterpolymers of dialkylfumarates, vinyl esters of fatty acids and alkylvinyl ethers. Pour point depressants useful for the purposes of thisinvention, techniques for their preparation and their uses are describedin U.S. Pat. Nos. 2,387,501; 2,015,748; 2,655,479; 1,815,022; 2,191,498;2,666,746; 2,721,877; 2,721,878; and 3,250,715 which are herebyincorporated by reference for their relevant disclosures.

Anti-foam agents are used to reduce or prevent the formation of stablefoam. Typical anti-foam agents include silicones or organic polymers.Additional anti-foam compositions are described in "Foam ControlAgents", by Henty T. Kerner (Noyes Data Corporation, 1976), pages125-162.

The sulfurized compositions of this invention can be added directly tothe lubricant. Preferably, however, they are diluted with asubstantially inert, normally liquid organic diluent such as mineraloil, naphtha, benzene, toluene or xylene, to form an additiveconcentrate. These concentrates usually contain from about 20% to about90% by weight of the sulfurized compositions of this invention and maycontain, in addition, one or more other additives known in the art ordescribed hereinabove. The remainder of the concentrate is thesubstantially inert normally liquid diluent.

The following examples illustrate the lubricant compositions of theinvention (including additive concentrates).

                  TABLE II    ______________________________________    Lubricants    (Parts by Weight)    Example      L-1     L-2     L-3   L-4   L-5    ______________________________________    Mineral Oil  98.58   98.75   98.57 98.14 98.64    Product of    Example 1    0.87    Example 3            1.0    Example 9                    0.94    Example 11                         1.25    Example 21                               0.87    Mixture of mono- and 0.25    di-para alkylated    diphenyl amines    Amine neutralized                 0.40            0.40  0.50  0.40    hydroxyalkyl dial-    kyl phosphorodi-    thioate    Polyoxyalkylene                 0.005           0.005 0.005 0.005    demulsifier    N--tridecyltri-                 0.05            0.05  0.05  0.05    methylene diamine    Tolyltriazole                 0.015           0.015 0.015 0.015    Silicone anti-                 0.02            0.02  0.04  0.02    foam agent    ______________________________________

While the invention has been explained in relation to its preferredembodiments, it is to be understood that various modifications thereofwill become apparent to those skilled in the art upon reading thespecification. Therefore, it is to be understood that the inventiondisclosed herein is intended to cover such modifications as fall withinthe scope of the appended claims.

I claim:
 1. A sulfurized composition prepared by the process whichcomprises sulfurizing a mixture comprising(A) at least one terpenecompound, and (B) at least one other olefinic compound of the formula:

    R.sup.1 R.sup.2 C═CR.sup.3 R.sup.4

wherein R¹, R², R³ and R⁴ are, independently, hydrogen or an organicgroup and the olefinic double bond is a non-aromatic double bond;wherein (A) and (B) are sulfurized in the presence of sulfur, sulfurhalide, or a mixture of sulfur or sulfur dioxide and hydrogen sulfide;and wherein the equivalent ratio of the mixture of (A) to (B) is fromabout 1:20 to about 10:1.
 2. The composition of claim 1 wherein (A)comprises at least one sulfurized terpene compound or a mixture of atleast one terpene compound and at least one sulfurized terpene compound.3. The composition of claim 1 wherein the terpene compound (A) comprisesa mixture of terpene hydrocarbons and their oxygen-containingderivatives.
 4. The composition of claim 1 wherein the terpene compoundis a turpentine, pine oil, or dipentene.
 5. The composition of claim 3wherein the oxygen-containing derivatives are terpene alcohols.
 6. Thecomposition of claim 4 wherein the terpene compound is a pine oil. 7.The composition of claim 1 wherein the other olefinic compound (B) is(i)at least one aliphatic, aryl aliphatic or alicyclic olefinic hydrocarboncontaining at least about 3 carbon atoms, (ii) at least one unsaturatedfatty acid or unsaturated fatty acid ester, (iii) at least onesulfurized derivative of (i) or (ii), or (iv) mixtures thereof.
 8. Thecomposition of claim 7 wherein the olefin (B) is at least one aliphaticolefinic compound.
 9. The composition of claim 8 wherein the olefiniccompound is at least one of propylene, isobutene, and dimers, trimers,tetramers and low molecular weight polymers thereof.
 10. The compositionof claim 1 wherein the other olefinic compound (B) is at least onealiphatic olefin containing from about 3 to about 36 carbon atoms. 11.The composition of claim 8 wherein the aliphatic olefin is at least onealpha-olefin.
 12. The composition of claim 11 wherein the alpha-olefincontains from about 3 to about 36 carbon atoms.
 13. The composition ofclaim 1 wherein the olefinic compound (B) comprises a mixture of atleast one alpha-olefin and at least one unsaturated fatty acid orunsaturated fatty acid ester.
 14. The composition of claim 1 wherein themixture is sulfurized by reaction with sulfur.
 15. The composition ofclaim 1 wherein the ratio of (A) to (B) is from about 1:10 to 2:1. 16.The composition of claim 1 wherein (A) is a sulfurized terpene andsulfurization is effected by heating the mixture.
 17. The composition ofclaim 1 wherein (B) is a sulfurized olefinic compound and sulfurizationis effected by heating the mixture.
 18. The composition of claim 1wherein (A) is at least one sulfurized terpene, (B) is at least oneother olefinic compound which is sulfurized, and sulfurization iseffected by heating the mixture.
 19. The composition of claim 1 whereinthe olefin (B) is at least one unsaturated fatty acid, unsaturated fattyacid ester, or mixtures thereof.
 20. The composition of claim 1 whereinthe mixture also contains a sulfurization promoter.
 21. A sulfurizedcomposition prepared by the process which comprises the steps of(A)preparing a mixture comprising sulfur and at least one terpene compound,(B) heating said mixture to a temperature of up to about 150° C. andmaintaining this temperature for a period of from about 2 to 20 hours,(C) raising the temperature of the mixture to up to about 200° C. whileremoving water and volatile materials, (D) adding at least one aliphaticolefinic compound to the mixture and maintaining the mixture at atemperature up to about 200° C. for a period of up to about 15 hours.22. The composition of claim 21 wherein about one equivalent of olefinis added per equivalent of terpene compound.
 23. The composition ofclaim 21 wherein the terpene compound is a pine oil.
 24. The compositionof claim 21 wherein the olefin compound is an alpha-olefin.
 25. Thecomposition of claim 21 wherein the olefin compound contains from about3 to about 36 carbon atoms.
 26. An additive concentrate comprising asubstantially inert, normally liquid diluent and about 20-90% by weightof the sulfurized composition of claim
 1. 27. An additive concentratecomprising a substantially inert, normally liquid diluent and about20-90% by weight of the sulfurized composition of claim
 21. 28. Alubricating composition comprising a major proportion of lubricating oiland a minor proportion, sufficient to improve the oxidation inhibitingproperties, of a sulfurized composition according to claim
 1. 29. Alubricating composition comprising a major proportion of lubricating oiland a minor proportion, sufficient to improve the oxidation inhibitingproperties, of a sulfurized composition according to claim 21.